U.S. patent application number 10/749825 was filed with the patent office on 2005-07-07 for color motion picture print film.
This patent application is currently assigned to Eastman Kodak Company. Invention is credited to Gisser, Kathleen R.C., Johnston, Brian H..
Application Number | 20050147933 10/749825 |
Document ID | / |
Family ID | 34711142 |
Filed Date | 2005-07-07 |
United States Patent
Application |
20050147933 |
Kind Code |
A1 |
Johnston, Brian H. ; et
al. |
July 7, 2005 |
Color motion picture print film
Abstract
Processing color motion picture film to yield a dye-only,
"silverless" soundtrack enables reduced silver levels to be
incorporated into all three color image records of a motion picture
print film while still providing a good soundtrack signal in the
resulting processed film. A silver halide light sensitive motion
picture photographic print element is disclosed comprising a
support bearing on one side thereof: a blue color sensitive, yellow
dye image-forming record comprising at least one blue-sensitive
silver halide emulsion having associated therewith yellow
dye-forming coupler; a red color sensitive, cyan dye image-forming
record comprising at least one red-sensitive silver halide emulsion
having associated therewith cyan dye-forming coupler; and a green
color sensitive, magenta dye image-forming record comprising at
least one green-sensitive silver halide emulsion having associated
therewith magenta dye-forming coupler; wherein each of the silver
halide emulsions have an average grain size of less than 1
micrometer and comprise at least 50 mol percent chloride, based on
silver, the silver halide emulsions in total comprise from 500-1350
mg/m.sup.2 silver, the cyan, magenta and yellow dye-forming
couplers are present at levels sufficient to provide visual
densities of at least 3.3 when completely consumed, the silver to
dye-forming coupler stoichiometric equivalent molar ratio in each
of the image-forming records is less than 1.4, and the silver to
dye-forming coupler stoichiometric equivalent molar ratio in at
least one of the image-forming records is less than 1.0.
Inventors: |
Johnston, Brian H.;
(Pittsford, NY) ; Gisser, Kathleen R.C.;
(Pittsford, NY) |
Correspondence
Address: |
Paul A. Leipold
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Assignee: |
Eastman Kodak Company
|
Family ID: |
34711142 |
Appl. No.: |
10/749825 |
Filed: |
December 31, 2003 |
Current U.S.
Class: |
430/505 ;
430/567 |
Current CPC
Class: |
G03C 7/3022 20130101;
G03C 5/04 20130101; G03C 7/3022 20130101; G03C 2001/03594 20130101;
G03C 7/3041 20130101; G03C 2007/3024 20130101; G03C 2007/3025
20130101; G03C 2001/03517 20130101; G03C 7/3041 20130101; G03C
2001/03594 20130101; G03C 7/3041 20130101; G03C 2007/3025 20130101;
G03C 2007/3024 20130101; G03C 2001/03517 20130101; G03C 7/3017
20130101 |
Class at
Publication: |
430/505 ;
430/567 |
International
Class: |
G03C 001/46 |
Claims
1. A silver halide light sensitive motion picture photographic
print element comprising a support bearing on one side thereof: a
blue color sensitive, yellow dye image-forming record comprising at
least one blue-sensitive silver halide emulsion having associated
therewith yellow dye-forming coupler; a red color sensitive, cyan
dye image-forming record comprising at least one red-sensitive
silver halide emulsion having associated therewith cyan dye-forming
coupler; and a green color sensitive, magenta dye image-forming
record comprising at least one green-sensitive silver halide
emulsion having associated therewith magenta dye-forming coupler;
wherein each of the silver halide emulsions have an average grain
size of less than 1 micrometer and comprise at least 50 mol percent
chloride, based on silver, the silver halide emulsions in total
comprise from 500-1350 mg/m.sup.2 silver, the cyan, magenta and
yellow dye-forming couplers are present at levels sufficient to
provide Visual densities of at least 3.3 when completely consumed,
the silver to dye-forming coupler stoichiometric equivalent molar
ratio in each of the image-forming records is less than 1.4, and
the silver to dye-forming coupler stoichiometric equivalent molar
ratio in at least one of the image-forming records is less than
1.0.
2. A print element according to claim 1, wherein the cyan, magenta
and yellow dye-forming couplers are present at levels sufficient to
provide Visual densities of at least 3.6 when completely
consumed.
3. A print element according to claim 1, wherein the cyan, magenta
and yellow dye-forming couplers are present at levels sufficient to
provide Visual densities of at least 3.8 when completely
consumed.
4. A print element according to claim 1, wherein silver halide
emulsions of the dye image-forming records comprise a total level
of from 500-1250 mg/m.sup.2 silver.
5. A print element according to claim 1, wherein silver halide
emulsions of the dye image-forming records comprise a total level
of from 800-1250 mg/m.sup.2 silver.
6. A print element according to claim 1, wherein silver halide
emulsions of the dye image-forming records comprise a total level
of from 800-1150 mg/m.sup.2 silver.
7. A print element according to claim 1, wherein silver halide
emulsions of the dye image-forming records comprise a total level
of from 900-1150 mg/m.sup.2 silver.
8. A print element according to claim 1, wherein the silver to
dye-forming coupler stoichiometric equivalent molar ratio in each
of the image-forming records is less than 1.3, and the silver to
dye-forming coupler stoichiometric equivalent molar ratio in at
least two of the image-forming records is less than 1.0.
9. A print element according to claim 1, wherein the silver to
dye-forming coupler stoichiometric equivalent molar ratio in each
of the image-forming records is less than 1.2, and the silver to
dye-forming coupler stoichiometric equivalent molar ratio in at
least two of the image-forming records is less than 0.9.
10. A print element according to claim 1, wherein the silver to
dye-forming coupler stoichiometric equivalent molar ratio in each
of the image-forming records is less than 1.2, and the silver to
dye-forming coupler stoichiometric equivalent molar ratio in at
least one of the image-forming records is less than 0.8.
11. A print element according to claim 1, wherein the silver to
dye-forming coupler stoichiometric equivalent molar ratio in each
of the image-forming records is less than 1.0.
12. A print element according to claim 1, wherein each of the
red-sensitive and green-sensitive silver halide emulsions comprise
emulsion grains having an average equivalent circular diameter of
less than 0.60 micron, and the blue-sensitive silver halide
emulsion comprises emulsion grains having an average equivalent
circular diameter of less than 1.0 micron.
13. A print element according to claim 1, wherein each of the
red-sensitive and green-sensitive silver halide emulsions comprise
emulsion grains having an average equivalent circular diameter of
less than 0.40 micron, and the blue-sensitive silver halide
emulsion comprises emulsion grains having an average equivalent
circular diameter of less than 0.80 micron.
14. A method for recording and processing image area frames and an
optical soundtrack in a color motion picture print film according
to claim 1, said method comprising: imagewise exposing the color
sensitive records in accordance with desired image area frames,
exposing at least one of the color sensitive records in accordance
with an analog soundtrack, and processing the exposed film in a
development amplification process to yield corresponding dye images
in the exposed image area frames and analog soundtrack; wherein
said film is processed to yield a dye-only, silverless analog
soundtrack, the soundtrack region of the film not being subjected
to any specialized processing treatment relative to the image area
frame region.
15. The method of claim 14, wherein the soundtrack is recorded and
developed in a single color record of the print film.
16. The method of claim 15, further comprising reading the
developed dye only soundtrack using a narrow band light source the
wavelength of which coincides with the peak absorbance wavelength
of the soundtrack dye.
17. The method of claim 15, wherein said soundtrack is exposed in
said single color record with a light source corresponding to the
peak sensitivity of the color record.
18. The method of claim 17, wherein said single color record is the
red-light sensitive color record and the exposing light source is a
red light emitting diode laser.
19. The method of claim 1, wherein the film processing comprises an
initial development step and a subsequent development amplification
step.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a color motion picture print silver
halide photographic film, and more particularly to such a film
which has reduced silver levels designed for processing in a redox
amplification development process. The invention further relates to
a method for recording and processing image area frames and an
optical soundtrack in such a color motion picture print film.
BACKGROUND
[0002] Color photographic silver halide materials are processed by
a process which includes a color development step. In conventional
color development, silver halide is reduced to metallic silver in
the light-exposed areas and the oxidized color developer formed in
this reaction then couples with a color coupler and forms image
dye. In such conventional development, the maximum amount or dye
produced is stoichiometrically proportional to the amount of silver
halide reduced to metallic silver, and the type of dye-forming
coupler employed. For so-called "2-equivalent" couplers, two mols
of silver are required to form one mol of dye. For "4-equivalent"
couplers, four mols of silver are required to form one mol dye.
[0003] In recent years there has been a trend to reduce the amount
of silver contained in photographic materials, while still
generating sufficient dye images. There are various reasons why
this has been done and these include reducing costs, reducing the
thickness of silver halide emulsion layers, gaining sharpness, and
improving the environmental impact. One class of low silver
photographic materials are color materials intended for redox
amplification processes wherein the developed silver acts as a
catalyst to the formation of dye image. Redox amplification
processes have been described, for example, in U.S. Pat. Nos.
3,674,490, 3,765,891, 3,822,129, 3,748,138, 4,088,486 and
4,954,425, and in Research Disclosure, December 1973, Page 109 No.
11660. In such processes, low silver containing color materials are
developed to produce a silver image and then treated with an
amplifying solution to form a dye image. The amplifying solution is
usually combined with the developer to form the so-called
developer-amplifier solution. The developer-amplifier solution
contains a reducing agent, for example a color developing agent,
and an oxidizing agent which will oxidize the color developing
agent in the presence of the silver image which acts as a catalyst.
The oxidized color developer reacts with a color coupler to form
the image dye. During amplification, the silver image is used to
produce greater quantities of oxidized developer by the action of
the oxidizing agent on the catalytic surface provided by the silver
image. The extra dye formed is said to amplify or intensify the
image. Hence smaller amounts of silver halide in the photographic
material are needed while still providing the desired image dye
density. The amount of image produced in redox amplification
processes depends on the time of treatment or the availability of
color coupler, and is less dependent on the amount of silver in the
image as is the case in conventional color development processes.
Examples of suitable oxidizing agents include peroxy compounds
including hydrogen peroxide, cobalt (III) complexes including
cobalt hexamine complexes, and periodates. Mixtures of such
compounds can also be used.
[0004] A serious problem with developer-amplifier solutions,
however, is their stability. Because they contain both an oxidizing
agent (e.g., the peroxide) and a reducing agent (the color
developing agent), they may react together spontaneously leading to
loss of activity in a short period of time. Various means to
stabilize the developer-amplifier processing solution have been
described. Such means include the use of metal sequestrants as
described in U.S. Pat. No. 5,702,873 which reduces the degree to
which metal ions catalyze the reaction of peroxide, the use of high
pH as described in U.S. Pat. No. 6,114,101 which slows the
oxidation reaction, the use of borate and silicate buffers as
described in U.S. Pat. Nos. 5,667,947 and 5,731,135, zinc ions as
described in U.S. Pat. No. 5,821,037 and the use of hydroxylamine
sulfate, as the anti-oxidant or preservative agent as described in
U.S. Pat. No. 6,303,279.
[0005] Alternatively, means to overcome the instability of the
developer-amplifier solution include modifications to commercial
photoprocessing tanks and equipment, for example the use of low
volume thin tanks has been described in U.S. Pat. Nos. 5,387,499,
5,361,114, 5,382,995, 5,319,410 and 5,475,461 that require use of
less than 1 liter and as little as 100 ml of solution permitting
the use of unstable processing chemistry. Indeed, substantial
effort has been applied to address the constraints bought on by the
use of a developer-amplifier that effective solutions employ
configurations where the ratio of tank volume to maximum area of
material accomodatable therein (i.e., maximum path length times
width of material) is less than 11 dm.sup.3/m.sup.2 and preferably
less than 3 dm.sup.3/m.sup.2.
[0006] An alternative to a single solution is where the developer
is used in a first bath followed by an amplifier bath. The amount
of dye formed in such a system, however, is limited by the amount
of color developing agent carried over into the second bath from
the first. In order to provide sufficient color developer solely
through carry-over, it would be necessary to have a level of color
developing agent in the developer bath that would be too high for
continuous running. U.S. Pat. No. 5,324,624 teaches the use of a
developer bath followed by a developer-amplification bath. While
not completely eliminating stability problems, use of the described
process has the effect of lowering the needed concentration of the
components of the developer-amplifier and contributing to improved
solution stability. In this way low silver reflective color print
materials are developed with
4-N-ethyl-N-(beta-methanesulfonamidoethyl)-o- -toluidine
sesquisulfate (color developer CD-3) as the specific color
developing agent under conditions suitable for the commercial use
of a color paper minilab photoprocessor.
[0007] Motion picture print film, the film that is shown in movie
theaters, commonly employs an optical analog soundtrack along an
edge of the film. During projection of the motion picture images, a
light source illuminates the analog soundtrack and a photosensor
senses the light passing through and modulated by the soundtrack to
produce an audio signal that is sent to amplifiers of the theater
sound system. While the most common soundtracks are of the
"variable area" type wherein the signal is recorded in the form of
a varying ratio of opaque to relatively clear area along the
soundtrack, "variable density" soundtracks are also known wherein
the absolute density is uniformly varied along the soundtrack.
Common sound systems incorporate a photodiode in the projector
whose radiant sensitivity peaks at approximately 800-950 nm
(depending on the type of photodiode), which detects the
predominant infra-red (IR) radiation emitted by common tungsten
lamps.
[0008] A dye soundtrack may be formed in color motion picture film
in accordance with conventional exposing and color development
processing. Such dye soundtracks may be formed in multiple
photosensitive emulsion layers of the motion picture film, or may
be restricted to a single emulsion layer as set forth in U.S. Pat.
No. 2,176,303. In order to provide effective modulation of common
projector soundtrack illumination light, however, motion picture
print film is typically processed according to a complex system
wherein the optical analog soundtrack area of the print film is
developed differently from the picture image frame area so that a
silver image is left in the soundtrack area of the film, whereas
all the silver is removed in the picture frame area, leaving only a
dye image. The silver image may be reformed selectively in the
soundtrack area of the film through selective application of a
second developer solution after initial uniform color development
(which develops exposed silver halide in both the picture area and
soundtrack area up to silver metal and generates image dye), stop
bath and fixer (arrests development and removes undeveloped silver
halide), and bleach (converts exposed, developed silver back to
silver halide in both the picture area and soundtrack area) steps.
The second development step typically comprises application of a
thick, viscous solution of a conventional black and white developer
with a cellulose compound such as nitrosyl in a stripe solely onto
the soundtrack area of the film, causing the silver halide in the
soundtrack area to be selectively developed back into silver metal,
while not affecting the silver halide in the image area. A
subsequent fixing step then removes the silver halide from the
image area, while leaving a silver image corresponding to the
soundtrack exposure. Various other techniques are also known for
retaining silver in the soundtrack area, but all such approaches
invariably entail certain processing disadvantages, such as
critical reactant concentration control and area-selective reactant
application requirements. Examples of such techniques, e.g., are
set forth in U.S. Pat. Nos. 2,220,178, 2,341,508, 2,763,550,
3,243,295, 3,705,799, and 4,139,382.
[0009] U.S. Pat. No. 4,219,615 suggests the use of a color
amplification development process for photographic films which
contain reduced silver levels in some, but not all of the emulsion
layers of the element, such that a sound track with a high silver
image may be formed in at least one layer of the element upon
processing. While the objective of providing photographic films
with overall reduced silver levels is obtained to a degree, the use
of a film with color records having both reduced and conventional
high silver levels introduces further complexities into color
balancing requirements, as the different color records may react
substantially differently to changes in process conditions.
Further, the proposed process and photographic elements do not
eliminate the need for special processing in the sound track area
relative to the scene image areas of the exposed film.
[0010] It has also been shown that where development amplification
processes are designed for processing low silver color papers, for
example those having about 200 mg/m.sup.2 or less of silver, such
processes generally cannot be used to process conventional color
papers that typically contain from 500 to 700 mg/m.sup.2 because
gross overamplification would occur. Similar compatibility problems
would be expected for processing of conventional relatively high
silver level motion picture print films with an amplified
development process designed specifically for use with relatively
low silver level color print films. U.S. Pat. No. 5,871,891 teaches
a means to process both low silver and conventional higher silver
photographic recording materials using the same processing
apparatus, where the developer solution is modified depending upon
the type of photographic material being processed. While such
technique may be practical for use in processing of color paper
materials when using processing apparatus employing relatively low
development solution volume, it would not be practical for use in
processing of motion picture color print films, which are typically
processed in apparatus employing relatively high solution
volumes.
[0011] It would be desirable to provide a color motion picture
print silver halide photographic film which has reduced silver
levels designed for processing in a redox amplification development
process, which meet desired requirements for color print films to
be viewed in transmission, typically illuminated by a xenon light
source, which materials must have uniquely high visual density and
neutrality in the Dmax. It would be further desirable to provide a
system and method for recording and processing such a reduced
silver color motion picture film having both image area frames and
an optical soundtrack which provides simplified processing
requirements.
SUMMARY OF THE INVENTION
[0012] We have found that by processing color motion picture film
to yield a dye-only, "silver-less" soundtrack, reduced silver
levels may be incorporated into all three color image records of a
motion picture print film while still providing a good soundtrack
signal in the resulting processed film. The invention enables
reduced silver levels to be employed in a print film, and a
simplified processing procedure which does not require special
processing of the exposed soundtrack relative to the image area
frames.
[0013] One embodiment of the invention is directed towards a silver
halide light sensitive motion picture photographic print element
comprising a support bearing on one side thereof: a blue color
sensitive, yellow dye image-forming record comprising at least one
blue-sensitive silver halide emulsion having associated therewith
yellow dye-forming coupler; a red color sensitive, cyan dye
image-forming record comprising at least one red-sensitive silver
halide emulsion having associated therewith cyan dye-forming
coupler; and a green color sensitive, magenta dye image-forming
record comprising at least one green-sensitive silver halide
emulsion having associated therewith magenta dye-forming coupler;
wherein each of the silver halide emulsions have an average grain
size of less than 1 micrometer and comprise at least 50 mol percent
chloride, based on silver, the silver halide emulsions in total
comprise from 500-1350 mg/m.sup.2 silver, the cyan, magenta and
yellow dye-forming couplers are present at levels sufficient to
provide visual densities of at least 3.3 when completely consumed,
the silver to dye-forming coupler stoichiometric equivalent molar
ratio in each of the image-forming records is less than 1.4, and
the silver to dye-forming coupler stoichiometric equivalent molar
ratio in at least one of the image-forming records is less than
1.0.
[0014] A second embodiment of the invention comprises a method for
recording and processing image area frames and an optical
soundtrack in a color motion picture film according to the first
embodiment by imagewise exposing the color sensitive records in
accordance with desired image area frames, exposing at least one of
the color sensitive records in accordance with an analog
soundtrack, and processing the exposed film in a development
amplification process to yield corresponding dye images in the
exposed image area frames and analog soundtrack; wherein said film
is processed to yield a dye-only, silverless analog soundtrack, the
soundtrack region of the film not being subjected to any
specialized processing treatment relative to the image area frame
region.
DETAILED DESCRIPTION
[0015] In motion picture color printing, there are usually three
records to record simultaneously in the image area frame region of
a print film, i.e., red, green and blue. The original record to be
reproduced is preferably an image composed of sub-records having
radiation patterns in different regions of the spectrum. Typically
it will be a multicolor record composed of sub-records formed from
cyan, magenta and yellow dyes. The principle by which such
materials form a color image are described in James, The Theory of
the Photographic Process, Chapter 12, Principles and Chemistry of
Color Photography, pp 335-372, 1977, Macmillan Publishing Co. New
York, and suitable materials useful to form original records are
described in Research Disclosure, December, 1987, Item 17643,
published by Industrial Opportunities Ltd., Homewell Havant,
Hampshire, P09 1EF, United Kingdom, and Research Disclosure,
September 1994, Item 36544, published by Kenneth Mason
Publications, Ltd., Emsworth, Hampshire P010 7DQ, England.
Materials in which such images are formed can be exposed to an
original scene in a camera, or can be duplicates formed from such
camera origination materials, such as records formed in color
negative intermediate films such as those identified by the
tradenames Eastman Color Intermediate Films 2244, 5244 and 7244.
The peak absorptions for such films are in the blue region of the
spectrum at about 440 nm, in the green region of the spectrum at
about 540 nm, and in the red region of the spectrum at about 680
nm.
[0016] The motion picture print film of the invention comprise a
support bearing on one side thereof: a blue color sensitive, yellow
dye image-forming record comprising at least one blue-sensitive
(approx. 380-500 nm) silver halide emulsion having associated
therewith yellow dye-forming coupler; a red color sensitive, cyan
dye image-forming record comprising at least one red-sensitive
(approx. 600-760 nm) silver halide emulsion having associated
therewith cyan dye-forming coupler; and a green color sensitive,
magenta dye image-forming record comprising at least one
green-sensitive (approx. 500-600 nm) silver halide emulsion having
associated therewith magenta dye-forming coupler. Each of the cyan,
magenta, and yellow image forming records may be comprised of a
single light-sensitive layer, a pack of two light-sensitive layers
with one being more light sensitive and the other being less
light-sensitive, or a pack of three or more light-sensitive layers
of varying light-sensitivity. These layers can be combined in any
order depending upon the specific features designed in the
photographic element. The element can contain additional layers,
such as filter layers, interlayers, overcoat layers, subbing
layers, antihalation layers, antistatic layers, and the like.
[0017] In the following discussion of suitable materials for use in
the emulsions and elements that can be used in conjunction with the
invention, reference will be made to Research Disclosure, September
1994, Item 36544, available as described above, which will be
identified hereafter by the term "Research Disclosure." The
contents of the Research Disclosure, including the patents and
publications referenced therein, are incorporated herein by
reference, and the Sections hereafter referred to are Sections of
the Research Disclosure, Item 36544.
[0018] Suitable silver halide emulsions and their preparation as
well as methods of chemical and spectral sensitization are
described in Sections I, and III-IV. Vehicles and vehicle related
addenda are described in Section II. Dye image formers and
modifiers are described in Section X. Various additives such as UV
dyes, brighteners, luminescent dyes, antifoggants, stabilizers,
light absorbing and scattering materials, coating aids,
plasticizers, lubricants, antistats and matting agents are
described, for example, in Sections VI-IX. Layers and layer
arrangements, color negative and color positive features, scan
facilitating features, supports, exposure and processing can be
found in Sections XI-XX.
[0019] Photographic light-sensitive elements may utilize silver
halide emulsion image forming layers wherein chloride, bromide
and/or iodide are present alone or as mixtures or combinations of
at least two halides. The combinations significantly influence the
performance characteristics of the silver halide emulsion. In
accordance with the invention, each of the light sensitive silver
halide emulsions employed in the image forming records of the print
film have an average grain size equivalent circular diameter (ECD)
of less than 1 micrometer (where the ECD of a grain is the diameter
of a circle having the area equal to the projected area of a grain)
and comprise at least 50 mol percent chloride (preferably at least
80 mol %, and more preferably at least 90 mol % chloride), based on
silver. The ECDs of silver halide emulsion grains employed in the
color print film elements of the invention are preferably less than
0.60 micron (more preferably less than 0.4 micron) in red and green
sensitized layers and less than 1.0 micron (more preferably less
than 0.8 micron) in blue sensitized layers. Such fine grain
emulsions used in print elements generally have an aspect ratio of
less than 1.3, where the aspect ratio is the ratio of a grain's ECD
to its thickness, although higher aspect ratio grains may also be
used. Such grains may take any regular shapes, such as cubic,
octahedral or cubo-octahedral (i.e., tetradecahedral) grains, or
the grains can take other shapes attributable to ripening,
twinning, screw dislocations, etc. Typically, print element
emulsions grains are bounded primarily by {110} crystal faces,
since {100} silver chloride grain faces are exceptionally stable.
Specific examples of high chloride emulsions used for preparing
photographic prints are provided in U.S. Pat. Nos. 4,865,962;
5,252,454; and 5,252,456, the disclosures of which are here
incorporated by reference.
[0020] Such relatively small, relatively high chloride emulsions
are preferred for low granularity performance and environmental
processing advantages. As explained in Atwell, U.S. Pat. No.
4,269,927, e.g., silver halide with a high chloride content
possesses a number of highly advantageous characteristics. For
example, high chloride silver halides are more soluble than high
bromide silver halide, thereby permitting development to be
achieved in shorter times. Furthermore, the release of chloride
into the developing solution has less restraining action on
development compared to bromide and iodide and this allows
developing solutions to be utilized in a manner that reduces the
amount of waste developing solution. Since print films are intended
to be exposed by a controlled light source, the imaging speed gain
which would be associated with high bromide emulsions offers little
benefit for such print films.
[0021] Photographic print films which comprise relatively small
grain, high chloride emulsions (e.g., emulsions having average
grain size equivalent circular diameters of less than about 1
micron and halide contents of greater than 50 mole % chloride) as
discussed above in order to optimize print image quality and enable
rapid processing typically result in relatively low speed
photographic elements in comparison to camera negative origination
films. Low speed is compensated for by the use of relatively high
intensity print lamps or lasers for exposing such print elements.
For comparison purposes, it is noted that motion picture color
print films, e.g., when rated using the same international
standards criteria used for rating camera negative films, would
typically have an ISO speed rating of less than 10, which is
several stops slower than the slowest camera negative films in
current use.
[0022] Couplers that may be used in the elements of the invention
can be defined as being 4-equivalent or 2-equivalent depending on
the number of atoms of Ag.sup.+ required to form one molecule of
dye. A 4-equivalent coupler can generally be converted into a
2-equivalent coupler by replacing a hydrogen at the coupling site
with a different coupling-off group. Coupling-off groups are well
known in the art. Such groups can modify the reactivity of the
coupler. Such groups can advantageously affect the layer in which
the coupler is coated, or other layers in the photographic
recording material, by performing, after release from the coupler,
functions such as dye formation, dye hue adjustment, development
acceleration or inhibition, bleach acceleration or inhibition,
electron transfer facilitation, color correction and the like.
Representative classes of such coupling-off groups include, for
example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy,
acyl, heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole,
alkylthio (such as mercaptopropionic acid), arylthio, phosphonyloxy
and arylazo. These coupling-off groups are described in the art,
for example, in U.S. Pat. Nos. 2,455,169; 3,227,551; 3,432,521;
3,476,563; 3,617,291; 3,880,661; 4,052,212 and 4,134,766; and in
U.K. Patents and published Application Nos. 1,466,728; 1,531,927;
1,533,039; 2,006,755A and 2,017,704A, the disclosures of which are
incorporated herein by reference.
[0023] Image dye-forming couplers may be included in elements of
the invention such as couplers that form cyan dyes upon reaction
with oxidized color developing agents which are described in such
representative patents and publications as: U.S. Pat. Nos.
2,367,531; 2,423,730; 2,474,293; 2,772,162; 2,895,826; 3,002,836;
3,034,892; 3,041,236; 4,883,746 and "Farbkuppler-Eine Literature
Ubersicht," published in Agfa Mitteilungen, Band III, pp. 156-175
(1961). Preferably such couplers are phenols and naphthols that
form cyan dyes on reaction with oxidized color developing agent.
Also preferable are the cyan couplers described in, for instance,
European Patent Application Nos. 544,322; 556,700; 556,777;
565,096; 570,006; and 574,948.
[0024] Couplers that form magenta dyes upon reaction with oxidized
color developing agent which can be incorporated in elements of the
invention are described in such representative patents and
publications as: U.S. Pat. Nos. 2,600,788; 2,369,489; 2,343,703;
2,311,082; 2,908,573; 3,062,653; 3,152,896; 3,519,429 and
"Farbkuppler-Eine Literature Ubersicht," published in Agfa
Mitteilungen, Band III, pp. 126-156 (1961). Preferably such
couplers are pyrazolones, pyrazolotriazoles, or
pyrazolobenzimidazoles that form magenta dyes upon reaction with
oxidized color developing agents. Especially preferred couplers are
1H-pyrazolo [5,1-c]-1,2,4-triazole and 1H-pyrazolo
[1,5-b]-1,2,4-triazole. Examples of 1H-pyrazolo
[5,1-c]-1,2,4-triazole couplers are described in U.K. Patent Nos.
1,247,493; 1,252,418; 1,398,979; U.S. Pat. Nos. 4,443,536;
4,514,490; 4,540,654; 4,590,153; 4,665,015; 4,822,730; 4,945,034;
5,017,465; and 5,023,170. Examples of 1H-pyrazolo
[1,5-b]-1,2,4-triazoles can be found in European Patent
Applications 176,804; 177,765; U.S. Pat. Nos. 4,659,652; 5,066,575;
and 5,250,400.
[0025] Couplers that form yellow dyes upon reaction with oxidized
color developing agent and which are useful in elements of the
invention are described in such representative patents and
publications as: U.S. Pat. Nos. 2,875,057; 2,407,210; 3,265,506;
2,298,443; 3,048,194; 3,447,928 and "Farbkuppler-Eine Literature
Ubersicht," published in Agfa Mitteilungen, Band III, pp. 112-126
(1961). Such couplers are typically open chain ketomethylene
compounds. Also preferred are yellow couplers such as described in,
for example, European Patent Application Nos. 482,552; 510,535;
524,540; 543,367; and U.S. Pat. No. 5,238,803.
[0026] To control the migration of various components coated in a
photographic layer, including couplers, it may be desirable to
include a high molecular weight hydrophobe or "ballast" group in
the component molecule. Representative ballast groups include
substituted or unsubstituted alkyl or aryl groups containing 8 to
40 carbon atoms. Representative substituents on such groups include
alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen,
alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino,
anilino, carbonamido (also known as acylamino), carbamoyl,
alkylsulfonyl, arysulfonyl, sulfonamido, and sulfamoyl groups
wherein the substituents typically contain 1 to 40 carbon atoms.
Such substituents can also be further substituted. Alternatively,
the molecule can be made immobile by attachment to a polymeric
backbone.
[0027] It may be useful to use a combination of couplers any of
which may contain known ballasts or coupling-off groups such as
those described in U.S. Pat. Nos. 4,301,235; 4,853,319 and
4,351,897.
[0028] In addition to the light sensitive dye forming layers, the
print film used in accordance with the invention may include
further features and layers as are known in the art. For example,
antihalation and antistatic layers may be included on either side
of the support, along with additional conventional interlayers and
overcoat layers. Preferred supports for the print films comprise
transparent polymeric films, such as cellulose nitrate and
cellulose esters (such as cellulose triacetate and diacetate),
polycarbonate, and polyesters of dibasic aromatic carboxylic acids
with divalent alcohols such as poly(ethylene terephthalate). It is
further specifically contemplated that the print elements of the
invention may comprise antihalation and antistatic layers and
associated compositions as set forth in U.S. Pat. Nos. 5,650,265,
5,679,505, and 5,723,272, the disclosures of which are incorporated
by reference herein. Alternatively, an antihaltion comprising a
hydrophilic colloid and silver as described in U.S. Pat. No.
5,753,402 may be employed. Antistatic layers comprising
polythiophene which exhibit a conductivity shift upon processing
such as described in U.S. Pat. No. 6,440,654, the disclosure of
which is incorporated by reference herein, are also specifically
contemplated. If desired, the print films can be used in
conjunction with an applied magnetic layer as described in Research
Disclosure, November 1992, Item 34390 published by Kenneth Mason
Publications, Ltd., Dudley House, 12 North Street, Emsworth,
Hampshire P010 7DQ, ENGLAND.
[0029] Further in accordance with the invention, the silver halide
emulsions employed in the image forming records of the print film
in total comprise from 500-1350 mg/m.sup.2 silver (preferably at
least 800 and more preferably at least 900 mg/m.sup.2, and
preferably at most 1250 and more preferably at most 1150
mg/m.sup.2), the cyan, magenta and yellow dye-forming couplers are
present at levels sufficient to provide visual densities of at
least 3.3 when completely consumed, the silver to dye-forming
coupler stoichiometric equivalent molar ratio in each of the
image-forming records is less than 1.4 (preferably less than 1.3,
and more preferably less than 1.2), and the silver to dye-forming
coupler stoichiometric equivalent molar ratio in at least one (and
preferably at least two) of the image-forming records is less than
1.0 (preferably less than 0.9, more preferably less than 0.8). Such
requirements define a unique motion picture print film which
enables the production of desirably high density images with good
granularity while employing low silver levels. If silver levels are
substantially below about 500 mg/m.sup.2, visual densities of
greater than 3.3 may be difficult to consistently and robustly be
obtained even with amplified development processing. If the silver
levels are above 1350, as well as if the silver to dye-forming
coupler stoichiometric ratios in one or more records are above the
stated requirements, advantages of reduced silver levels are
compromised. Visual densities of at least 3.3 (preferably at least
3.6, and more preferably at least 3.8) are required to provide
sufficient black densities.
[0030] For the purposes of the invention, the silver to dye-forming
coupler stoichiometric ratio is defined as the ratio of the mols of
silver halide to the moles of dye-forming coupler in a particular
color record, divided by the equivalency of the dye-forming coupler
(i.e., divided by 2 for 2-equivalent couplers, and divided by 4 for
4-equivalent couplers). Coupler equivalency is well-known and
established in the photographic art. In contrast to the present
invention, in conventional print films intended for processing with
conventional development, in order to account for development
inefficiencies while also enabling coupling of substantially all
imaging coupler employed, the silver to dye-forming coupler
stoichiometric equivalent molar ratio in each of the image-forming
records is typically greater than 1.0, and is further typically
greater than 1.2 (commonly greater than 1.3 and frequently greater
than 1.4) in at least one (and commonly in at least two) of the
image-forming records. The print films of the invention
specifically employ relatively lower ratios of silver to the amount
of image forming couplers present.
[0031] In accordance with one embodiment of the invention, the
image area frame region of the print film is conventionally
imagewise exposed to produce a latent image in the red, green and
blue light photosensitive layers of the print film. The soundtrack
region of the print film is exposed to produce a latent image
corresponding to an analog soundtrack in at least one
photosensitive layer of the print film. While the analog sound
track may be recorded in more than one photosensitive layer of the
print film (e.g., in both the red and green light sensitive layers
as is conventionally practiced), in a preferred embodiment of the
invention the exposure is limited to a single photosensitive layer
through choice of soundtrack exposing light, filters, etc. In a
most preferred embodiment of the invention, only the red light
photosensitive cyan dye forming layer is exposed in accordance with
the analog soundtrack. This may be conveniently done through use of
a red light emitting diode laser in recording the soundtrack.
[0032] After the motion picture print films are exposed, they are
processed in accordance with one embodiment of the present
invention with a redox amplification development process employing
an oxidizing agent in combination with a color developing agent to
form a visible color image in the image area frame region of the
film and a silverless "dye only" analog soundtrack. Processing a
silver halide color photographic light-sensitive material in
accordance with the invention is basically composed of 1) amplified
color development and 2) desilvering.
[0033] As described in the prior art, examples of suitable
oxidizing agents for use in redox amplified development processes
include peroxy compounds including hydrogen peroxide, cobalt (III)
complexes including cobalt hexamine complexes, and periodates.
Amplified color development of color print films in accordance with
the present invention may be achieved by modifying conventional
color print film development processes, which typically will employ
KODAK Color Developing Agent CD-2 (N,N-diethyl p-phenylenediamine
sulfate) as more fully described in Kodak Publication No. H-24,
Manual For Processing Eastman Color Films, the disclosure of which
is hereby incorporated by reference, by the incorporation of the
oxidizing agent in the main developer solution step, or in a pre-
or post-developer processing bath. In accordance with a preferred
embodiment, the oxidizing agent is introduced in a development
amplifier step conducted after a main color developer step, as more
fully discussed in co-pending, concurrently-filed, commonly
assigned U.S. Ser. No. ______ (Kodak Docket No. 84785), the
disclosure of which is incorporated by reference herein. While
conventional development processing of current commercially
available color print films results in processing efficiency (E)
values typically of less than 2.5 (where (E) values are calculated
using the formula: E=(Dye Image Dmax)/(Silver coverage,
g/m.sup.2)), in such preferred process, relatively low silver color
print films such as those of the present invention may be processed
to provide processing efficiency (E) values of from 2.5 to 6.7,
more preferably 2.5 to 5.0 and most preferably 3.0 to 5.0, while
also maintaining visual Dmin less than 0.1 and the Equivalent
Neutral Density (END) Dmax values for the cyan and yellow color
records within 20% (more preferably within 15% and most preferably
within 10%) of the END Dmax value for the green color record, which
is desired for obtaining adequate color balance when developed
print film images are projected with a xenon light source. END
value for any particular dye color record is defined as the visual
density that results when the other two dyes are added in
quantities just sufficient to produce a neutral gray (see, e.g.,
"Procedures for Equivalent-Neutral-Density (END) Calibration of
Color Densitometers Using a Digital Computer", by Albert J. Sant,
in the Photographic Science and Engineering, Vol. 14, Number 5,
September-October 1970, pg. 356).
[0034] The desilvering stage comprises a bleaching step to change
the developed silver back to an ionic-silver state and a fixing
step to remove the ionic silver from the light-sensitive material.
The bleaching and fixing steps can be combined into a monobath
bleach-fix step that can be used alone or in combination with the
bleaching and the fixing step. If necessary, additional processing
steps may be added, such as a washing step, a stopping step, a
stabilizing step and a pretreatment step. The processing chemicals
may be liquids, pastes, or solids, such as powders, tablets or
granules.
[0035] Print film processing in accordance with one embodiment of
the invention is characterized in that the soundtrack region of the
film is not subjected to any specialized processing treatment
relative to the image area frame region. As previously explained,
the formation of a silver sound track on a color motion picture
film in accordance with conventional practice requires additional
special processing steps to retain the silver solely in the sound
track region of the film, which are not needed in accordance with
the present invention. Such processing is described for the Kodak
ECP-2D Process, e.g., in Kodak Publication No. H-24, Manual For
Processing Eastman Color Films, the disclosure of which is hereby
incorporated by reference. Such previously performed steps no
longer needed in accordance with the invention include, e.g.,
soundtrack drying, soundtrack applicator, soundtrack developer, and
soundtrack spray rinse steps. A dye only soundtrack is simply
developed in the soundtrack region of the print film as the dye
images are formed in the image area frame region.
[0036] Due to the spectral differences between the silver and the
dye only soundtracks, in accordance with a further preferred
embodiment of the invention, the projector systems currently used
for films containing silver soundtracks are modified for use with
the motion picture print films exposed and processed in accordance
with the invention to contain a dye-only soundtrack to improve the
performance of the dye-only soundtrack. Most existing sound motion
picture projectors incorporate a photodiode in the projector whose
radiant sensitivity peaks at approximately 800-950 nanometers
(depending on the type of photodiode) to detect the predominant
infra-red (IR) radiation emitted by the tungsten lamp and modulated
by the film's variable area silver soundtrack. A dye only sound
track, however, will modulate light predominantly in the visible
region of the spectrum. Although the photodiodes have some
sensitivity in the visible range (approximately 380-760 nanometers)
of the radiation spectrum, their lower sensitivity in this range,
coupled with the lower emission of the light source in the visible
range results in a very low input to the sound amplifier. The
situation is further aggravated by the fact that the density range
between the "clear" minimum density (Dmin) area and the "opaque"
maximum density (Dmax) area of a variable area analog soundtrack is
less for the dye only soundtrack. If the signal is too low for the
amplification stage to operate properly (e.g. signal-to-noise
loss), the sound quality will be degraded.
[0037] Improved performance for the dye-only soundtracks of the
invention can be achieved, e.g., by using the modified soundtrack
interface apparatus for a motion picture projectors as described in
U.S. Pat. No. 5,483,306, the disclosure of which is hereby
incorporated by reference. Alternatively, or additionally, improved
performance for the dye-only soundtracks of the invention can be
achieved by recording and developing the soundtrack in a single
photosensitive layer of the print film, and recovering the signal
from the dye only soundtrack using a narrow band (e.g., 10-30 nm
bandwidth) light source the wavelength of which is chosen so as to
coincide with the peak absorbance wavelength of the soundtrack dye.
Where the cyan layer of the print film is used to record the
soundtrack, e.g., a narrow band red light source would be used for
reading the developed soundtrack. A red light emitting diode may be
conveniently used for reading cyan dye-only soundtracks, e.g., as
has been recently proposed by Dolby Laboratories in an announcement
at the Association of Cinema and Video Laboratories (ACVL) Jun.
1-3, 1995 convention at Lake Tahoe, Nev. The use of such relatively
monochromatic light sources for the soundtrack reader in
combination with a single layer dye soundtrack maximizes the
relative optical density difference between the dyed areas and the
undyed transparent areas of the soundtrack while maintaining high
contrast. While a conventional tungsten light source may perform
poorly with a dye only soundtrack due to the relatively low signal
generated in the solar cell of the soundtrack reader resulting from
the poor modulation of the tungsten light by the image dyes, the
use of a narrow monochromatic light source eliminates the presence
of unmodulated light outside the absorbance spectrum of the dye
only soundtrack striking the solar cell, thereby improving the
modulation signal generated by the solar cell.
[0038] The following examples illustrate preparation of
photographic elements of the present invention, and their
beneficial characteristics.
COMPARISON EXAMPLE 1
[0039] This example demonstrates the typical range of visual Dmax,
Silver content and Efficiency of conventional commercially
available color print films when processed according to the
manufacturer's recommendations.
[0040] Commercially available color print film elements 101, 102,
103, and 104 were exposed for {fraction (1/500)}s on a 1-B
sensitometer with a 3200K light source and a 0-3 LogE step tablet,
and then processed in the standard color print process ECP-2D as
described in the Kodak Publication H-24, Module 9; using a
persulfate bleach, omitting the first fix and subsequent wash, and
without any sound track application. The ECP-2D process employed
comprised a Color Developer step (3'), stop bath (40"), wash (40"),
bleach accelerator (20"), persulfate bleach (40"), wash (40"), fix
(40"), wash (1'), final rinse (10"), and then drying with hot air.
Processing of the exposed elements is done with the color
developing solution adjusted to 36.7.degree. C. (98 F). The
stopping, fixing, bleaching, washing, and final rinsing solution
temperatures are adjusted to 26.7.degree. C. (80 F).
[0041] The ECP-2D Color Developer comprises:
1 Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL
salt of nitrilo-tri(methylene phosphonic acid) Sodium sulfite
(anhydrous) 4.35 g Sodium bromide (anhydrous) 1.72 g Sodium
carbonate (anhydrous) 17.1 g Kodak Color Developing Agent, CD-2
2.95 g Water to make 1 liter pH @ 26.7.degree. C. is 10.53 +/-
0.05
[0042] The visual Dmax was calculated from the Status A red, green
and blue values according to the method in ISO Standard 5-3, using
the standard Illuminant A. Silver content was measured by
wavelength dispersive X-ray Fluorescence in unprocessed film. The
efficiency is calculated by the following equation: (1000*Visual
Dmax)/(Silver Content, mg/m.sup.2), and represents the amount of
silver that is necessary to achieve a particular Visual Density.
Higher efficiencies are desirable because the minimum amount of
silver in the film may be used to reach the desired Dmax.
2 TABLE 1 Visual Silver Content Element Dmax (mg/m.sup.2)
Efficiency 101 3.80 1636 2.32 102 4.75 2389 1.98 103 3.61 1453 2.48
104 3.27 1377 2.37
[0043] Elements 101-104 demonstrate that useful levels of Visual
Dmax (3.27 to 4.7) are currently accessible with commercially
available relatively high silver coverage (greater than 1350
mg/m.sup.2) films that have efficiencies below 2.5 when processed
with standard color print development process ECP-2D.
EXAMPLE 2
[0044] Comparison photographic color print film Element 105 (total
silver halide emulsion coverage 1471 mg/m.sup.2, based on silver)
was prepared according to the following formulation:
3 Protective Overcoat Gelatin 976 Polydimethylsiloxane lubricant
(Dow Corning) 16 Polymethylmethacrylate beads 16 Spreading Aids
Green Emulsion Layer AgClBr cubic grain emulsion GE-1, 1.35% Br,
0.14 micron, 68 spectrally sensitized with green sensitizing dye
GSD-1, 0.363 mmole/Ag mole, and green sensitizing dye GSD-2, 0.012
mmole/Ag mole. AgClBr cubic grain emulsion GE-2, 1.2% Br, 0.18
micron, 316 spectrally sensitized with green sensitizing dye GSD-1,
0.293 mmole/Ag mole, and green sensitizing dye GSD-2, 0.009
mmole/Ag mole. AgClBr cubic grain emulsion GE-3, 1.7% Br, 0.26
micron, 57 spectrally sensitized with green sensitizing dye GSD-1,
0.273 mmole/Ag mole, and green sensitizing dye GSD-2, 0.008
mmole/Ag mole. Magenta Dye Forming Coupler M-1 648 Green Filter Dye
GFD-2 54 Oxidized Developer Scavenger Scav-1 16 Gelatin 1426
Interlayer Oxidized Developer Scavenger Scav-1 48 Gelatin 610
Spreading aids Red Emulsion Layer AgClBr cubic grain emulsion RE-1,
0.8% Br, 0.14 micron, 60 spectrally sensitized with red sensitizing
dye RSD-1, 0.042 mmole/Ag mole. AgClBr cubic grain emulsion RE-2,
0.9% Br, 0.18 micron, 218 spectrally sensitized with red
sensitizing dye RSD-1, 0.044 mmole/Ag mole. AgClBr cubic grain
emulsion RE-3, 0.9% Br, 0.26 micron, 122 spectrally sensitized with
red sensitizing dye RSD-1, 0.050 mmole/Ag mole. Cyan dye forming
coupler C-1 888 Red Absorber Dye 63 Gelatin 2859 Interlayer
Oxidized Developer Scavenger Scav-1 48 Gelatin 610 Spreading aids
Blue Emulsion Layer AgClBr cubic grain emulsion BE-1, 0.4% Br, 0.40
micron, 126 spectrally sensitized with blue sensitizing dye BSD-1,
0.151 mmole/Ag mole and blue sensitizing dye BSD-2, 0.149 mmole/Ag
mole. AgClBr cubic grain emulsion BE-2, 0.5% Br, 0.50 micron, 297
spectrally sensitized with blue sensitizing dye BSD-1, 0.219
mmole/Ag mole and blue sensitizing dye BSD-2, 0.217 mmole/Ag mole.
AgClBr cubic grain emulsion BE-3, 0.3% Br, 0.90 micron, 208
spectrally sensitized with blue sensitizing dye BSD-1, 0.124
mmole/Ag mole and blue sensitizing dye BSD-2, 0.122 mmole/Ag mole.
Yellow Coupler (Y-1) 1315 Blue filter dye BFD-1 30 Yellow Preformed
Dye YPD-1 7 Gelatin 2395 Antihalation Layer Antihalation Filter Dye
AFD-1 56 Antihalation Filter Dye AFD-2 129 Gelatin 759 Spreading
aids Support Transparent polyethylene terephthalate support with
polyurethane overcoated Baytron P .TM. (available from Bayer
Corporation) antistatic layer on the back of the film base which
provides process surviving antistatic properties.
[0045] The following structures represent compounds utilized in the
above described photographic element. 1234
[0046] Photographic color print film Elements 106-109 in accordance
with the invention (total silver halide emulsion coverage 500-1350
mg/m.sup.2, based on silver) and Comparison Element 110 (total
silver halide emulsion coverage 490 mg/m.sup.2, based on silver)
were prepared similarly to Element 105, but by varying the silver
levels, coupler level and emulsion levels as indicated in Table 2A
below:
4TABLE 2A (Laydowns in mg/m.sup.2) Green Red Blue Emulsion,
Emulsion, Emulsion, (Percent (Percent (Percent GE-3, GE-2, Magenta
RE-3, RE-2, Cyan BE-3, BE-2, Yellow Element GE-1) Coupler RE-1)
Coup BE-1) Coupler 105 442 648 400 888 632 1315 (15.5, 71.5, 13)
(15, 54.5, 30.5) (20, 47, 33) 106 368 619 330 844 510 1258 (15.5,
71.5, 13) (15, 54.5, 30.5) (20, 49.5, 30.5) 107 344 648 311 888 491
1315 (15.5, 71.5, 13) (15, 54.5, 30.5) (20, 47, 33) 108 339 664 279
817 452 1304 (13, 80, 7) (0, 81.5, 18.5) (0, 80, 20) 109 245 648
222 888 351 1315 (15.5, 71.5, 13) (15, 54.5, 30.5) (20, 47, 33) 110
147 648 133 888 210 1315 (15.5, 71.5, 13) (15, 54.5, 30.5) (20, 47,
33)
[0047] Elements 105-110 were processed according to an amplified
development process comprising a Color Developer I step (1'), an
Amplifier I step (1'), stop bath (40"), wash (40"), bleach
accelerator (20"), persulfate bleach (40"), wash (40"), fix (40"),
wash (1'), final rinse (10"), and then drying with hot air.
Processing of the exposed elements is done with the color
developing and amplifier solutions adjusted to 36.7.degree. C. The
stopping, fixing, bleaching, washing, and final rinsing solution
temperatures are adjusted to 26.7.degree. C.
[0048] The Color Developer I comprises:
5 Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL
salt of nitrilo-tri(methylene phosphonic acid) Sodium sulfite
(anhydrous) 4.35 g Sodium bromide (anhydrous) 1.3 g Sodium
carbonate (anhydrous) 17.1 g Kodak Color Developing Agent, CD-2 3.1
g Sulfuric acid (7.0N) 0.62 mL Water to make 1 liter pH @
26.7.degree. C. is 10.65 +/- 0.05
[0049] The Amplifier I comprises:
6 Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL
salt of nitrilo-tri(methylene phosphonic acid) Sodium carbonate
(anhydrous) 17.1 g H.sub.2O.sub.2 (30%) 12 g Color Developer I 80
mL Water to make 1 liter pH @ 26.7.degree. C. is 10.8 +/- 0.05
[0050] After processing, the visual density and efficiency were
measured as described above. The films were then read for Status A
densitometry, and to calculate the color balance, the Status A
densitometry was converted to Equivalent Neutral Densitometry using
the method as described in the article "Procedures for
Equivalent-Neutral-Density (END) Calibration of Color Densitometers
Using a Digital Computer", by Albert J. Sant, in the Photographic
Science and Engineering, Vol. 14, Number 5, September-October 1970,
pg. 356-362. The END values for the highest density step are
reported in the Table 2B below.
7TABLE 2B Ag/ Coup Total Silver Equiv Silver Color mg/ Coupler mol
END Visual mg/ Elem. Rec. m.sup.2 mg/m.sup.2 ratio Dmax Dmax
m.sup.2 E 105 Green 440 648 0.97 4.05 3.94 1471 2.68 Red 396 888
1.06 3.69 Blue 635 1316 1.46 3.90 106 Green 368 619 0.85 4.06 3.92
1208 3.25 Red 330 844 0.93 3.65 Blue 510 1258 1.23 3.77 107 Green
342 648 0.76 4.06 3.91 1144 3.42 Red 308 888 0.82 3.65 Blue 494
1316 1.14 3.82 108 Green 339 664 0.73 3.80 3.80 1070 3.55 Red 279
817 0.81 3.70 Blue 452 1304 1.05 3.79 109 Green 245 648 0.54 3.51
3.73 817 4.57 Red 220 888 0.59 3.63 Blue 353 1316 0.81 3.59 110
Green 147 648 0.32 2.75 2.70 490 5.51 Red 132 843 0.37 2.57 Blue
212 1304 0.49 2.71
[0051] Example 2B shows that visual densities at Dmax of at least
3.3 can be easily achieved for print elements having total silver
level above 500 mg/m.sup.2, with efficiencies between 2.5 and 6.7.
All of the inventive examples also have adequate color balance with
the END Dmax of the red and blue records within 20% of the END Dmax
of the green record.
[0052] Element 108 demonstrates that within the scope of the
invention, changes to the distribution of the silver and coupler
between the red, green, and blue sensitive layers, as well as the
ratio of emulsion types may be used to adjust the color balance at
Dmax.
EXAMPLE 3
[0053] Elements 109 and 110 were processed similarly as described
in as described in Example 2, except employing Color Developer II
in place of Color Developer I, and Amplifier II in place of
Amplifier I.
[0054] The Color Developer II comprises:
8 Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL
salt of nitrilo-tri(methylene phosphonic acid) Sodium sulfite
(anhydrous) 4.35 g Sodium bromide (anhydrous) 0.5 g Sodium
carbonate (anhydrous) 17.1 g Kodak Color Developing Agent, CD-2 3.7
g Sulfuric acid (7.0N) 0.62 mL Water to make 1 liter pH @
26.7.degree. C. is 10.65 +/- 0.05
[0055] The Amplifier II comprises:
9 Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL
salt of nitrilo-tri(methylene phosphonic acid) Sodium carbonate
(anhydrous) 17.1 g H.sub.2O.sub.2 (30%) 15 g Color Developer II 10
mL Water to make 1 liter pH @ 26.7.degree. C. is 10.8 +/- 0.05
[0056] The results obtained are reported in Table 3:
10 TABLE 3 Visual Silver Content Element Dmax (mg/m.sup.2)
Efficiency 110 3.78 490 7.71 109 3.94 817 4.82
[0057] The above data demonstrates that process changes may be used
to enhance the efficiency of the elements with the lowest silver
content. By altering the process, the efficiency of comparison
element 110, e.g., may be increased until the visual Dmax is within
the desired range for a print film. However, a wide variability of
the Dmax dependent upon process changes is not necessarily
desirable, as motion picture films are generally processed in large
laboratories and the film is expected to be perform relatively
invariant to process changes. While Element 109 within the scope of
the invention demonstrates some process dependency, it does so to a
much less extent.
EXAMPLE 4
[0058] Typically, reducing the silver in an element processed in a
standard development process reduces the speed and the contrast of
the film to an unacceptable level. This is demonstrated by a
comparison of commercially available color print film Element 101
(1636 mg/m.sup.2 silver) and Element 107 in accordance with the
invention (1144 mg/m.sup.2 silver) processed without amplification
as described in Example 1. In an amplified process, Element 107 in
accordance with the invention regains its speed, as demonstrated by
the processing of Element 107 through an amplified development
process as described in Example 2, and even surpasses
conventionally processed Element 101 by more than half a stop in
the blue record, as indicated by the data in Table 4, where delta
speed is 100 times the difference in loge necessary to reach
density of 1.0. However, the contrast of element 107 is even lower
after amplified development than it is in the non-amplified
process. By adjusting the ratio of the emulsions, as well as the
amount of silver and coupler in each color record, however, as done
in Element 108, the speed of a reduced silver print film element
may be made to remain higher than that of the conventionally
processed Element 101, while achieving contrasts within 5% of such
conventional element. In combination with the Dmax levels of
Element 108 (from Example 2 above) this insures that acceptable
images may be obtained on the screen. Since contrast also affects
granularity, the granularity (.sigma..sub.d) and contrast for
Elements 101, 107 and 108 were measured at a density of 1.0 and
(1000*.sigma..sub.d/contrast) as reported in the Table 4 below.
11 TABLE 4 (1000 * .sigma..sub.d/ Average grain .DELTA. Speed at
.DELTA. contrast (%) contrast) at size (microns) Density = 1.0 at
Density = 1.0 Density = 1.0 Element Process R G B R G B R G B R G B
101 Ex. 1 -- -- -- 0 0 0 0.0 0.0 0.0 5.78 6.02 14.63 107 Ex. 1 0.18
0.18 0.55 -13 -16 -12 -11.5 -16.0 -20.3 6.72 7.21 21.90 107 Ex. 2
0.18 0.18 0.55 4.1 -2 23 -24.5 -21.2 -28.5 7.13 6.47 30.22 108 Ex.
2 0.17 0.19 0.48 3 6 17 -1.4 -3.8 4.7 5.44 5.27 11.08
[0059] On a contrast-normalized basis, the granularity of Element
107 is worse (higher) than that of Element 101 when processed
through the standard ECP-2D process. The disparity is even worse in
the red and blue records when Element 107 is processed through the
amplified process described in Example 2. Reducing granularity is
most easily done by reducing the grain size, but this reduces the
photographic speed of the element. Because the speed of Elements
107 and 108 in the amplified process are faster than that of
Element 101 in the ECP-2D process, the blend ratio of the emulsions
may be changed to reduce the amount of fast emulsion, and in the
case of the blue record, to substantially reduce the average grain
size in the layer without falling below the desired speed. The
resulting granularity of Element 108 when processed in the
amplified process is comparable to that of Element 101 when
conventionally processed through ECP-2D.
EXAMPLE 5
[0060] Color print film Elements 106-109 described in Example 2 are
imagewise exposed in accordance with desired image area frames, and
the cyan dye forming layer is exposed in accordance with a variable
area analog soundtrack. The exposed films are then processed
according to the amplified development process described in Example
2 to yield corresponding dye images in the image area frames, and a
dye-only, silverless analog soundtrack. The films yield acceptable
results for sensitometry, halation latitude, sharpness, and
graininess. The film also yields acceptable audio performance for a
dye-only soundtrack.
[0061] While the invention has been described in detail with
particular reference to preferred embodiments, it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *